Compositions for flame-proofing cellulosic materials

ABSTRACT

FIRE RESISTANCE AND WRINKLE RESISTANCE ARE IMPARTED TO CELLULOSIC MATERIALS BY TREATEMENT WITH N,N&#39;&#39;,N&#34;-TRIALLYL PHOSPHORIC TRIAMIDE WITHOUT ADVERSELY AFFECTING OTHER PROPERTIES OF THE CELLULOSIC MATERIALS. THE TREATING COMPOSITIONS AND THE TREATED ARTICLE ARE ALSO DISCLOSED.

United States Patent 3,715,185 COMPOSITIONS FOR FLAME-PROOFINGCELLULOSIC MATERIALS Joseph A. Meyers III, Springfield, and Joseph A.Cahill,

Philadelphia, Pa., assignors to Atlantic Richfield Company,Philadelphia, Pa.

No Drawing. Original application Oct. 30, 1970, Ser. No. 85,815, nowPatent No. 3,666,402, dated May 30, 1972. Divided and this applicationDec. 30, 1971, Ser.

Int. Cl. D06m 13/44 US. Cl. 8-194 4 Claims ABSTRACT OF THE DISCLOSUREFire resistance and Wrinkle resistance are imparted to cellulosicmaterials by treatment with N,N',N"-triallyl phosphoric triamide withoutadversely affecting other properties of the cellulosic materials. Thetreating compositions and the treated article are also disclosed.

This is a division of application Ser. No. 85,815 filed Oct. 30, 1970,now Pat. No. 3,666,402.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to a wash-durable single step aqueous bath treatment forcellulosic textiles which renders them tire and wrinkle resistant.

Description of the prior art It is known that flame resistant propertiescan be imparted to cellulosic materials (textile fabrics) by treatmentwith phosphorus containing compounds. Organic phosphorus compoundscontaining functional groups capable of chemically reacting with thecellulose are used when it is desired that the flame resistantproperties be durable to a number of laundering cycles. See for exampleGuth, U.S. 3,421,923, issued Jan. 14, 1969; Reeves et al., US.2,809,941, issued Oct. 15, 1957; Glade et al., US. 2,828,- 228, issuedMar. 25, 1958; Chance et al., US. 3,403,044, issued Sept. 24-, 1968; andReeves et al., U.S. 3,276,897, issued Oct. 4, 1966. It is also knownthat introduction of nitrogen in a phosphorus-containing flame retardanthas a synergistic effect. See Tesoro et al., Textile Research Journal,1969, pp. 180-190 who show N-hydroxymethyl-3-(dialkylphosphono)propionamide (NMPA) as a cellulose flame retardant.Also see Beninate et al., American Dyestuff Reporter, Dec. 2, 1968, pp.74-77, showing tetrakis (hydroxymethyl) phosphonium hydroxide inequilibrium with the tris (hydroxymethyl) phosphine, cured with ammoniato introduce nitrogen. The textile materials are impregnated usuallywith aqueous solutions containing the organic phosphorous compounds,dried and then subjected to conditions which insolubilize the flameretardant in situ. While such an impregnation materially improves theproperties of the heavier fabrics, it is often diflicult to obtain thedesired degree of flame resistance in the lighter weight fabrics withoutadversely altering other properties of the fabric. For example, it isoften diflicult to impart fire resistance to fabrics of less than about7 ounces per yard without causing an undesirable increase in thestiifness of the fabric. It is also difiicult to impart to any fabric anappreciable increase in both wrinkle resistance and flame resistance. Inorder to obtain both flame resistance and wrinkle resistance, thetextile material was usually treated successively with a flame retardantand then with a compound capable of imparting wrinkle resistantproperties. A single treatment process to impart both flame retardancyand wrinkle resistance has been long sought after in the art.

3,715,185 Patented Feb. 6, 1973 "'ice An object of the present inventionis to provide an improved method for treating textile fabrics so as toimprove their flame resistance to a greater degree than prior art flameretardancy methods at equal add on" levels. A second object is tosimultaneously impart wrinkle resistant and flame resistant propertiesto cellulosic textiles without materially increasing the fabricstiffness. Another object is to provide textile treating compositioncomprising a compound containing both phosphorus and nitrogen by whichboth the wrinkle resistance and the flame resistance of a textile can beenhanced by a single treatment. An additional object is to providetreated cellulosic textile materials which are both flame and wrinkleresistant at low add on levels. The present invention comprises treatinga textile material with a solution containing N,N',N"-triallylphosphorictriamide, drying to remove excess solvent, and then either curing atelevated temperatures in the presence of a catalyst or irradiating inwith a radio active source material to produce a wrinkle resistant andflame resistant textile fabric.

DETAILED DESCRIPTION OF THE INVENTION AND DESCRI P'TEON OF THE PREFERREDEMBODIMENTS Textile materials which may be modified include thosederived from cellulosic materials such as cotton, linen, rayon, jute,ramie, paper and the like. Blends of these with synthetic fabrics arealso very suitable. The N,N,N"- triallylphosphoric triamide is preparedby reacting phosphorous oxychloride with allylamine in a non-aqueoussolvent in the presence of a tertiary amine to react with the liberatedhydrochloric acid. The preferred mole ratio of both the allylamine andthe tertiary amine to phosphorous oxychlorlde is 3 to 1. Higher ratioscan be used although no advantage has been found to be gained.

Any inert non-aqueous solvent can be used. Suitable solvents include theether type such as diethyl ether or dioxane and the hydrocarbon typesuch as hexane, benzene, toluene, etc. The tertiary amine functions asan HCl acceptor and can be any trialkyl, alkyl-aryl, or heterocyclictype. Examples of trialkyl amines are triethyl amine, tripropyl amine,and tributyl amine. Examples of alkyl-aryl type are diethylphenyl amine.Examples of heterocyclic type are pyridine and pyrrole.

The reaction between the phosphorous oxychloride and allyl-amine isexothermic and generally it has been found to be desirable to controlthe reaction temperature below 50 C., and preferably between 5-25 C. Thetemperature control of the reaction may be conveniently carried out byutilizing a relatively slow addition rate for the reactants or bycooling the reaction mixture.

The HCl which is liberated during reaction reacts with the tertiaryamine to form the HCl salt which precipitates during reaction and iseasily removed from the reaction by filtration. The desiredN,N',N-triallylp'hosphoric triamide is recovered by removal of thesolvent and excess reactants by any suitable means such as vacuumdistillation.

Following reaction, the N,N, "-triallylphosphoric triamide can beformulated into the desired treating composition. Any suitableformulation can be used, for example, an emulsion or solution, withaqueous solution being generally preferred. The treating solution can beapplied to the fabric by dipping, spraying, rolling, padding or the liketechniques, as are known to those skilled in the art. Following theapplication of the treating formulation so as to impregnate the textilematerial, the excess of the formulation can be removed by squeezing,centrifuging, pressing, or other similar operations. The material can,if desired, be dried and is then cured by holding the treated textilematerial for several minutes at high temperatures or for several hoursat lower temperatures, or in the presence of a radioactive source forseveral minutes.

In formulating the textile treating composition theN,N','N"-triallylphosphoric triamide is included in the erably attemperatures within the range of about 150 to 180 C. At thesetemperatures, curing times of from 15 to 30 minutes are typical. Analternative embodiment is irradiating the cellulosic textile materialwhich has been formulation in amounts within the range of 1 to 50 per- 5contacted with a solution or emulsion of N,N',N"tricent by weight of thecomposition and preferably in allylphosphoric triamide with aradioactive material such amounts within the range of to 20 percent byweight as cobalt. In this embodiment the free radical catalyst is of thetotal composition. Additionally, it has been found unnecessary since theradiation acts as the polymerizato be desirable to also include in thetreating composition agent. tion a catalyst capable of initiating a freeradical polym- 10 It is believed that the N,N',N"-triallylphosphorictrierization by itself or in the presence of an activator such amide andthe cellulosic material react through the oleas a reducing agent. Suchredox systems are described in finic double bonds and the CH linkagesresp Fundamental Principles of Polymerization, DAlelio, sulting incross-linkage of the cellulosic material and the Gaetano F., John Wiley& Son, New York, 1950. Such i p g of Wrinkle resistance therebycatalystis desirably contained in the composition in The following examplesillustrate several embodiments amounts within the range of about 0.1 toabout perof the invention, but are not to be considered limiting. centby weight of the formulation and preferably in amounts within the rangeof about 0.5 to 10 percent by EXAMPLE I weight f the heating composition171 grams (3.0 moles) of allyl amine, 309 grams 3.05 Suitable compoundswhich can be used as the catalyst 20 moles) of triothylamino, and 1600of other were include hydrogen peroxide; persulfates h as ammoplaced ina Pyrex glass reaction vessel. The vessel was Ilium, sodium Potassium;hydroperoxides Such as flushed with nitrogen and the contents cooled toabout butyl hydroperoxide, cumene hydroperoxide; diacylper- Tooroaftor153-4 grams mole) of Phosphorous oxides such as henzoyl pcroxide, acetyiperoxide; di aikyi oxychloride were added dropwise over a two hourperiod. peroxides Such as dhhhutyi peroxide and dicumyi peroih Thetemperature of the reaction mixture was not allowed ide; peresters suchas t-butyl peroxyacetate, t-butyl perto go above Afior the addition oftho Phosphorous oxybenzoate; and peracids such as performic or hermeticoxychlonde the reaction mixture was stirred at ambient The remainder fthe textile treating compositioh is temperature for 2 hours and thenfiltered to remove the comprised of solvent and wetting agent, thelatter being P1' oo1Pit"1tocl triothylamino'Hcl Salt- Tho filtrate wasoptional. Suitable solvents include water, hexane, bensurfed about 16hours at ambient temperature with zene ethyl alcohol methyl alcohol, andany others Which 20 grams of decolorizing charcoal and then filtered todo not react with the N,N',N' triaiiyiphosphoric remove the latter. Thefiltrate was then vacuum distilled i Wetting agents such as Triton X400Which is to remove the ether solvent and excess reactants as overanethylene oxide aikyi Phenol adduct can he incorho head and the desiredproduct, N,N',N-triallylphosphoric rated in the treating composition inamounts ranging up mamido Q grams), was recovered as distillation io 5weight Pei-chm, preferably 05 to 1 Weight percehh toms. The Isolatedproduct was found to be greater than The textile treating formulationsare applied so as to 95 Percent Pure by elemental and NMRanalysesprovide in the textile material an add-on desirably withinEXAMPLE II the range of about 1 to 20 percent by weight of the textilematerial and preferably within the range of about 5 40 Atexfllentreiiltmg bath was.mad.e y combmmg 20 Parts to 15 percent byweight after the treated fabric has been of tnallylphosphonc mamldePrepared in cured The term refers to the flame retardant ample I a d twoparts of tertiary butyl hydroperoxide as Which has reacted with thetextile material; that is, the a free radical catalyshwith sufficientwater to make atotal modifying agent which remains as an integralchemical of 00 parts treatmg Solution Swatches of bleached Part of thematerial after curing and washing to remove desized, mercerrzed cottonprint cloth weighing 4 ounces any umeacted excess. The amount of adchonis given in per yard were then padded through this solution and a wetpercent by weight based on the original dry weight of the i' on thefabnc of 100 Percent was obtained After textile materialdry1ng, thetreated fabrics were then cured for 15 minutes The curing of the treatedtextile material is carried at 165 and then Washed under hot water toremove unreacted compound. out in one embodiment by holdmg the materialat tem- S peratures between about room temperature, i.e., about i attreats were made In whlch he textlle ireatmg 25 C., and about 250 C. fora period of time suflicient WIIS refluxed fk pnor to treatmg the topermit the reaction between the textile material and {lcs' This w doneto lnltlCite a low degree of Polymer" the y p p triamide to take placeiaatlon. All the treated fabr cs were tested for fire re- This period oftime can range from several hours at g g 3 the A.ATCC flame test methodroom temperature to several minutes at elevated temg figf gg ggg ifi g gg wrinkle peratures. Desirably the curing is carried out at temperaarestandard tests used by th: t tit t i o inc lust r I l t tures within therange of about to 250 C, and prefare given in Table 1. y. e resu 8 TABLE1 Cure conditions Weight Vertical Wrinkl Temp. dpyerggiiti telsghchhrrecoverly Treating solution l Time C.) on i h z' w l fi?giigggeilghtton--. l Bel 190 A 6.0 165 6.5 165 7.6 165 8.3 165 8.3 1658.5 165 9.1 ii? iii Not heat treated 16 hours..- 125 12. 3

20 wt. percent N N N"-trial1ylphos horie trlamid l 6.6 inch char leng'thallowable for 4 0 2 per yard of ceitio iif percent t butylhydroperoxide.

8 Burned entire length.

It can be seen that the add-ons obtained by the nonheat treated solutionranged from 6 to 7.5 percent by weight of the untreated fabric. Thefabrics containing 6.5 and 7.5 weight percent add-ons passed thevertical flame test as the char lengths obtained were 4.5 inches. A charlength of 5.5 inches is allowable by the test for cotton of this weight.Untreated cotton is consumed in the vertical flame test. Slightly higheradd-ons were obtained in the range of 8.5 to 10.5 weight percent whenthe treating solution was heat treated prior to impregnation of thefabrics. All of the treated fabric in this add-on range passed thevertical flame test. The flame resistance obtained at this level ofadd-on (7 weight percent) is considered quite good for the lightweightcotton being tested since add-ons in the range of to weight percent areusually required to give this degree of flame resistance for fabrics ofcomparable weight when prior art phosphorous flame retardants are used.There was no detectable difference between the hand of the treatedfabrics and the hand of the untreated fabric.

It can also be seen from Table 1 that the fabrics containing add-ons inthe range of 9 to 10.5 weight percent had wrinkle resistant propertiesas the dry wrinkle recovery values were 240 to 250 (W+F) as compared toabout 190 for untreated cotton.

EXAMPLE III The procedure of Example II was repeated with the exceptionthat longer curing times were used. In one case the treated fabric wascured for 1 hour at 165 C. and this resulted in an add-on of 14.2 weightpercent (Table 1). The treated fabric passed the vertical flame test andhad a wrinkle recovery angle of 271 Curing at longer times (18 hours) atlower temperatures (125) resulted in an add-on of 12.3 weight percent.The treated fabric passed the vertical flame test and had a wrinklerecovery value of 276.

EXAMPLE IV A textile treating bath was made by combining 20 parts ofN,N',N-triallylphosphoric triamide prepared in Example I With sufficientwater to make a total of 100 parts of treating solution. Swatches ofuntreated cotton fabric used in Example II were padded through thissolution and a wet pick-up on the fabric of 100% was obtained. Afterdrying the fabrics were then cured at room temperature by being exposedto a cobalt 60 radiation source with an effective exposure dose rate of250,000 roentgens per hour. After irradiation the fabrics were washedunder hot water to remove unreacted N,N',N"-triallylphosphoric triamide.

Dry add-ons of 1.5, 2.3 and 4.0 weight percent were obtained after thetreated fabrics were exposed to irradiation dosages of 0.25, 1.0 and 4.0megarads, respectively. This example shows thatN,N',N-trial1ylphosphoric triamide can be reacted with cotton usingionizing radiation as the free radical initiator and that the extent ofreaction with cotton is related to the irradiation dosage.

Textile fabrics treated to impart flame resistant prop erties normallyrequire high add-ons (15 percent or higher) which usually increase thestiffness of the fabric with no improvement in the wrinkle resistantproperties of the fabric. Tesoro et al., supra, at p. 182, required a17.1% add-on of NMPA to achieve a degree of fire retardancy (6.8 inchchar length) which does not even pass the AATCC vertical flame testwhich only allows 5.5 inches of char length for 4 ounces per yardfabric. Our flame retardant passed this test with only 6.5 weightpercent add-on (Table 1) and so appears to be mankedly superior thanNMPA in flame retardancy. A two step process consisting of treatment ofthe fabric with a flame retardant and then with a compound capable ofimparting wrinlkle resistance is usually required when a fabriccontaining both properties is desired.

In the present invention a textile fabric is treated with one compoundin a single step to produce a treated fabric having improved wrinkleresistant and fire resistant properties with no increase in stiffness ofthe fabric. The addon required to impart these properties is alsoexceptionally low.

Although the invention has been described above with great specificity,various modifications should become readily apparent to those skilled inthe art without departing from the spirit and scope of the invention.

We claim:

1. A textile treating composition comprising from 1 to 50 weight percentN,N',N"-triallylphosphoric triamide, 0.1 to 20 weight percent freeradical catalyst, 0 to 5 weight percent wetting agent, and the remaindersolvent.

2. The textile treating composition of claim 1 wherein the solvent isselected from the group consistng of water, hexane, benzene, ethylalcohol and methyl alcohol.

3. The textile treating composition of claim 1 wherein the compositioncomprises from 10 to 20 weight percent N,N',N"-trially1phosphorictriamide, 0.5 to 10 weight percent free radical catalyst, 0.5 to 1Weight percent wetting agent, and 89 to 69 weight percent water.

4. The composition of claim 1 wherein the free radical catalyst ist-butyl hydroperoxide.

References Cited UNITED STATES PATENTS 5/ 1972 Meyers et al. 8116.25/19-72 Cahill et al. 8116.2

OTHER REFERENCES Chemical Abstracts, 1963, vol. 58, p. 1485 (h).

GEORGE F. LESMES, Primary Examiner J. C. CANNON, Assistant Examiner US.Cl. X.R.

